CN106632895A - 3D printing light-cured resin composition activated by epoxidized limonene - Google Patents
3D printing light-cured resin composition activated by epoxidized limonene Download PDFInfo
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- CN106632895A CN106632895A CN201610877259.3A CN201610877259A CN106632895A CN 106632895 A CN106632895 A CN 106632895A CN 201610877259 A CN201610877259 A CN 201610877259A CN 106632895 A CN106632895 A CN 106632895A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 32
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229940087305 limonene Drugs 0.000 title claims abstract description 12
- 235000001510 limonene Nutrition 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 3
- 238000001723 curing Methods 0.000 claims description 37
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 11
- 238000000016 photochemical curing Methods 0.000 claims description 11
- 238000006735 epoxidation reaction Methods 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical class C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000012663 cationic photopolymerization Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 229940125810 compound 20 Drugs 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 150000002924 oxiranes Chemical group 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 13
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 abstract 1
- 239000012949 free radical photoinitiator Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 description 2
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000005839 radical cations Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- -1 poly- ammonia Ester Chemical class 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a 3D printing low-viscosity and hybrid light-cured resin composition activated by epoxidized limonene. The 3D printing light-cured resin composition contains a compound capable of performing cationic light curing and containing epoxy groups, a compound capable of performing free radical light curing and containing acrylate groups, ferrocene type cationic photoinitiator with carbazole groups, a free radical photoinitiator and an epoxidated limonene cationic light curing accelerator. The 3D printing light-cured resin composition can be rapidly cured under the irradiation of LED light sources of 405 nm and 395 nm to form a shaped object having excellent physical and mechanical properties.
Description
Technical field
The present invention relates to 3D printing technique field, and in particular to a kind of composition of 3D printing light curing resin composition and its
Application in 3D printing.
Background technology
Photo-curing material has quick solidifying, need not heat, can be made into solvent-free products, saves energy and easily realize automatic
The advantages of changing operation, is a green environmental protection technique.Photopolymerization shaping class 3D printing technique is that one kind utilizes photosensitive resin material
The general designation of the 3D printing technique of curing molding under light illumination, it mainly includes three kinds of technology paths：The first is by the U.S.
3DSystems develops and realizes earliest business-like Stereolithography technology (SLA)；It two is public by German envision TEC
Department is processed based on digital light and develop on the basis of (DLP) porjector technology DLP 3D printing techniques；It three is by Israel Objet
The polymeric spray technology (PolyJet) of company's (merging with Stratasys for 2012) exploitation.Three kinds of technologies are to photopolymerization group
The viscosity of compound, curing rate and curing materials performance etc. propose very high requirement.
Material for photocureable rapid shaping is liquid photocurable resin, or claims liquid photosensitive resin, main to include together
Polymers, reactive diluent and light trigger.According to the triggering mechanism of light trigger, light-cured resin can be divided three classes：From
By base light-cured resin, cation photocuring resin, mix type light-cured resin.The development trend of photocurable quick shaping process
It is to use to mix type light-cured resin.Its advantage mainly includes：When cyclic polymer carries out cation ring-opening polymerization, volume contraction
Very little even produces expansion, and free radical system always has significantly contraction, and mixing type system can be designed to shrinkage-free polymerization
Thing；Cation can still cause polymerization after illumination disappears, thus hybrid systems can overcome free radical fast deactivation after illumination disappearance and
The shortcoming for making polymerization terminate.
The application of radical UV curing system compared with cationic photocuring system, with initiator type is more and solidification
The advantages of speed is fast, so selecting in the composition for mixing curing system, performed polymer, the monomer of selectable commercialization
It is more with initiator type, and it is respectively provided with the fast advantage of curing rate.The initiator type of cation photocuring system is selected
It is less, mainly there are salt compounded of iodine, sulfosalt and the luxuriant class initiator of molysite three at present.Compared with free radical type photocuring system, sun from
The laser curing velocity of subtype photocuring system is slower, and the light absorbs of business-like salt compounded of iodine and sulfosalt exist
Below 350nm, it is impossible to meet the requirement of such as 395nm and 405nm visible light sources 3D printing light rapidform machine.Luxuriant swage sun from
Sub-light initiator prepares simple, and by the change of dispensing structure its ultraviolet-ray visible absorbing peak position can be regulated and controled, and from different spokes
Penetrate light source to match.The performed polymer that can be used for cation fixed line is mainly epoxy resin, and the epoxy pre-polymerization of better performances at present
As long as body bisphenol type epoxy and diglycidyl ether type epoxy, and the photopolymerization speed of both epoxides is slower.
Because the laser curing velocity of free radical system and cationic system is seriously mismatched so that in free radical-cation
There is free radical system rapid curing in hybrid UV curable paint and the solidification of cationic light-cured resin is incomplete, moulding material
Performance can not meet the serious problems of requirement, and rapid shaping tree of the patent with regard to radical-cation hybrid system is had at present
Fat is different degrees of to have this, makes curing materials performance not reach use requirement.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of fast rapid-result for 3D printing etc.
The light-curable resin of type technology, the curing rate of free radical type light-cured components and cationic light-cured components in resin
Curing rate is basically identical, therefore curing materials have the advantage of radical UV curing and cation photocuring concurrently, and the resin is one
Plant advanced Photocurable composition.
In order to achieve the above object, the technical solution used in the present invention is：
One specific admixture type 3D printing light curing resin composition, including following components by mass percentage：Cation
Gel-type resin component 20%-60%；Radical-curable resin Composition 15%-50%；Radical photoinitiator 0.1%-
10%；With carbazole group cyclopentadienyl swage cationic photoinitiator 0.1%-10%；Epoxidation limonene cationic photopolymerization promotees
Enter agent 0.1%-5%.
The cationic curing type resin Composition includes following components by mass percentage：Epoxy resin ingredient 50-
90%；Containing the monomeric compound 10-50% that epoxide group and/or the fourth oxyalkyl of ring four are rolled into a ball；The epoxy resin includes fat
Race's epoxy resin or aromatic epoxy resin.
The radical-curable resin Composition includes following components by mass percentage：Acrylate component
50-90%；Phosphate-based acrylic monomers compound 5-30%；Acrylate monomer compound 5- containing morpholine group
30%；The acrylate component includes the one of epoxy acrylate, urethane acrylate and polyester acrylate
Plant or mixture.
It is described as follows with carbazole group cyclopentadienyl swage cation light initiator general structure：
Wherein, R1, R2, R3 are selected from：- H- ,-R ', phenyl, halogen ,-OH ,-OR ' ,=R ', ≡ R ', the R ' of halo ,-R '
COO- or-R ' CONHR ", wherein R ' for C1-12 alkyl or alkylidene, R " for C1-12 alkyl or aryl, n is the whole of 0-4
Number；Q is selected from B, P, As, or Sb；X is halogen atom；M is the integer that the valence state of Q plus 1.
The cationic photopolymerization accelerator is epoxidation limonene, and structure is as follows：
One specific admixture type 3D printing light curing resin composition, including following components by mass percentage：Shrink sweet
Oily ether epoxy resin 20%-50%, 3,4- epoxycyclohexyls -3 ', 4 '-epoxycyclohexyl formic acid esters 5-30%, polyurethane propylene
Acid resin 10-60%, containing one or more phosphate-based acrylic monomers compound 5-10%, the propylene containing morpholine group
Acid ester monomer compound 5-30%, N- ethyl carbazole cyclopentadienyl molysite 0.1%-10%, 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change phosphine 0.1%-10%, epoxidation limonene 0.1%-10%.
A kind of three-D moulding object, the three-D moulding object is obtained by the shaping of type 3D printing light curing resin composition is mixed,
The article shaped adopts photocuring 3D printing moulding process, the 3D printing light curing resin composition to include by weight percent
The following components of meter：Bisphenol A epoxide resin 30%, 3,4- epoxycyclohexyls -3 ', 4 '-epoxycyclohexyl formic acid esters 20%, poly- ammonia
Ester acrylic resin 20%, containing one or more phosphate-based acrylic monomers compound 5%, the propylene containing morpholine group
Acid ester monomer compound 20%, N- ethyl carbazoles cyclopentadienyl molysite 3%, TMDPO 1%, ring
Limonene oxide 1%.
The present invention superiority be：The invention provides a specific admixture type 3D printing light curing resin composition, using sun
Ion and the dual light-cured components of free radical type, curing materials performance has that cubical contraction is low, physical and mechanical properties is excellent
Advantage；Using the luxuriant molysite with carbazole group as trigger for optical solidification, because having longwave absorption so as to can with 395nm with
Upper light source matches, while using the sensitizing of carbazole group, the velocity of initiation for making cationic componentses is improved；The present invention adopts ring
, used as cation photocuring accelerator, the tertiary carbon epoxy radicals with open loop in the compound molecule can for limonene oxide
Make the curing rate of cation photocuring component harmonious with the curing rate of radical UV curing component, aggregate into densification
Network structure；Said composition can be applied to the rapid forming equipments such as various photo-polymerization type 3D printings.
Specific embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment 1
Mix type 3D printing light curing resin composition：Bisphenol A epoxide resin 30%, 3,4- epoxycyclohexyls -3 ', 4 ' -
Epoxycyclohexyl formic acid esters 20%, polyurethane acrylic resin 20%, HEMA phosphate 5%, propylene
Morpholide 20%, N- ethyl carbazoles cyclopentadienyl molysite 3%, TMDPO 1%, epoxidation lemon
Alkene 1%.
The manufacturing process of this solidified resin is：Now light trigger is added in reactive diluent, then again 40-60 DEG C
Light trigger is dissolved in water-bath transparent, is eventually adding bisphenol A epoxide resin and polyurethane acrylic resin, stirring mixing 1-
2 hours.
The liquid laser fast shaping resin, in 25 DEG C of temperature, viscosity is 253mpa.s, good leveling property, using 405nm
LED/light source, it is possible to achieve 5-10s is fully cured.
Embodiment 2
Mix type 3D printing light curing resin composition：Bisphenol A epoxide resin 30%, 3,4- epoxycyclohexyls -3 ', 4 ' -
Epoxycyclohexyl formic acid esters 20%, bisphenol-A acrylic resin 20%, HEMA phosphate 5%, acryloyl
Morpholine 20%, N- ethyl carbazoles cyclopentadienyl molysite 3%, TMDPO 1%, epoxidation limonene
1%.
The manufacturing process of this solidified resin is：Now light trigger is added in reactive diluent, then again 40-60 DEG C
Light trigger is dissolved in water-bath transparent, is eventually adding bisphenol A epoxide resin and polyurethane acrylic resin, stirring mixing 1-
2 hours.
The liquid laser fast shaping resin, in 25 DEG C of temperature, viscosity is 287mpa.s, good leveling property, using 405nm
LED/light source, it is possible to achieve 5-10s is fully cured.
The physical and mechanical properties of material after the solidification of the 3D printing light curing resin composition of table one
Claims (7)
1. a specific admixture type 3D printing light curing resin composition, including following components by mass percentage：
Cationic curing type resin Composition 20%-60%
Radical-curable resin Composition 15%-50%
Radical photoinitiator 0.1%-10%
With carbazole group cyclopentadienyl swage cationic photoinitiator 0.1%-10%
Epoxidation limonene cationic photopolymerization accelerator 0.1%-5%.
2. type 3D printing light curing resin composition is mixed as claimed in claim 1, it is characterised in that the cationic curing
Type resin Composition includes following components by mass percentage：
Epoxy resin ingredient 50-90%
Containing the monomeric compound 10-50% that epoxide group and/or the fourth oxyalkyl of ring four are rolled into a ball, the epoxy resin includes fat
Race's epoxy resin or aromatic epoxy resin.
3. type 3D printing light curing resin composition is mixed as claimed in claim 1, it is characterised in that the radically curing
Type resin Composition includes following components by mass percentage：
Acrylate component 50-90%
Phosphate-based acrylic monomers compound 5-30%
Acrylate monomer compound 5-30% containing morpholine group, the acrylate component includes propylene oxide
One kind or mixture of acid esters, urethane acrylate and polyester acrylate.
4. type 3D printing light curing resin composition is mixed as claimed in claim 1, it is characterised in that described with carbazyl
The luxuriant swage cation light initiator general structure of group is as follows：
Wherein, R1, R2, R3 are selected from：- H- ,-R ', phenyl, halogen ,-OH ,-OR ' ,=R ', ≡ R ', the R ' of halo ,-R ' COO-
Or-R ' CONHR ", wherein R ' for C1-12 alkyl or alkylidene, R " for C1-12 alkyl or aryl, n is the integer of 0-4；Q
Selected from B, P, As, or Sb；X is halogen atom；M is the integer that the valence state of Q plus 1.
5. type 3D printing light curing resin composition is mixed as claimed in claim 1, it is characterised in that the cationic photopolymerization gathers
Conjunction accelerator is epoxidation limonene, and structure is as follows：
6. a specific admixture type 3D printing light curing resin composition, including following components by mass percentage：
Tetraglycidel ether epoxy resin 20%-50%
3,4- epoxycyclohexyls -3 ', 4 '-epoxycyclohexyl formic acid esters 5-30%
Polyurethane acrylic resin 10-60%
Containing one or more phosphate-based acrylic monomers compound 5-10%
Acrylate monomer compound 5-30% containing morpholine group
N- ethyl carbazoles cyclopentadienyl molysite 0.1%-10%
TMDPO 0.1%-10%
Epoxidation limonene 0.1%-10%.
7. a kind of three-D moulding object, the three-D moulding object is obtained by the shaping of type 3D printing light curing resin composition is mixed, institute
Article shaped is stated using photocuring 3D printing moulding process, the 3D printing light curing resin composition is included by mass percentage
Following components：
Bisphenol A epoxide resin 30%
3,4- epoxycyclohexyls -3 ', 4 '-epoxycyclohexyl formic acid esters 20%
Polyurethane acrylic resin 20%
Containing one or more phosphate-based acrylic monomers compounds 5%
Acrylate monomer compound 20% containing morpholine group
N- ethyl carbazoles cyclopentadienyl molysite 3%
TMDPO 1%
Epoxidation limonene 1%.
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| CN201610877259.3A CN106632895A (en) | 2016-10-09 | 2016-10-09 | 3D printing light-cured resin composition activated by epoxidized limonene |
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| CN201610877259.3A CN106632895A (en) | 2016-10-09 | 2016-10-09 | 3D printing light-cured resin composition activated by epoxidized limonene |
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| CN108191410A (en) * | 2018-01-23 | 2018-06-22 | 北京化工大学 | A kind of 3D printing is molded cation photocuring type aluminium oxide ceramics paste compound |
| CN109988273A (en) * | 2019-04-03 | 2019-07-09 | 北京石油化工学院 | A kind of preparation method of 3D printing long wave ultraviolet light curing resin composition |
| EP3680263A1 (en) * | 2019-01-14 | 2020-07-15 | Basf Se | Limonene-based (meth)acrylates for use in 3d printing |
| CN111690096A (en) * | 2020-05-20 | 2020-09-22 | 广西春景环保科技有限公司 | Preparation method of 3D printing photosensitive resin material |
| CN115418190A (en) * | 2022-10-04 | 2022-12-02 | 烟台大学 | Potting adhesive for low-temperature ultraviolet printed circuit board |
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2016
- 2016-10-09 CN CN201610877259.3A patent/CN106632895A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191410A (en) * | 2018-01-23 | 2018-06-22 | 北京化工大学 | A kind of 3D printing is molded cation photocuring type aluminium oxide ceramics paste compound |
| EP3680263A1 (en) * | 2019-01-14 | 2020-07-15 | Basf Se | Limonene-based (meth)acrylates for use in 3d printing |
| WO2020148189A1 (en) | 2019-01-14 | 2020-07-23 | Basf Se | Limonene-based (meth)acrylates for use in 3d printing |
| CN109988273A (en) * | 2019-04-03 | 2019-07-09 | 北京石油化工学院 | A kind of preparation method of 3D printing long wave ultraviolet light curing resin composition |
| CN109988273B (en) * | 2019-04-03 | 2021-08-10 | 北京石油化工学院 | Preparation method of long-wave ultraviolet curing resin composition for 3D printing |
| CN111690096A (en) * | 2020-05-20 | 2020-09-22 | 广西春景环保科技有限公司 | Preparation method of 3D printing photosensitive resin material |
| CN115418190A (en) * | 2022-10-04 | 2022-12-02 | 烟台大学 | Potting adhesive for low-temperature ultraviolet printed circuit board |
| CN115418190B (en) * | 2022-10-04 | 2023-06-06 | 烟台大学 | Potting adhesive for low-temperature ultraviolet light printed circuit board |
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Application publication date: 20170510 |